GB814288A - Manufacture and use of new aldehyde condensation products - Google Patents

Abstract

A non-cyclic compound containing at least once the atomic grouping <FORM:0814288/IV (a)/1> is first condensed at above 100 DEG C. with an aldehyde and a salt of an aliphatic amine containing at least two primary or secondary amino groups, and product is condensed in a second stage with an aldehyde and a water-soluble ammonium or amine salt in presence of a solvent. Suitable acyclic nitrogen compounds are dicyandiamide, dicyandiamidine, guanidine, acetoguanidine, biguanide, or substitution products thereof such as alkyl or aryl-biguanides. Formaldehyde is preferred. Other aldehydes, e.g. acetaldehyde or acrolein may be used. Preferably paraformaldehyde is used in the first stage and concentrated aqueous formaldehyde in the second. Suitable salts of polyamines are with organic or inorganic acids, preferably hydrochlorides or sulphates of ethylene diamine; 1,3-propylene diamine; hexamethylene diamine or alkyl or oxyalkyl substitution products of diamines; diethylene triamine; triethylene tetramine; tetraethylene pentamine or polyalkylene polyamines of higher molecular weight. Also suitable are salts obtained by heating an ethylene dihalide or glycerine dichlorhydrin with ammonia or an amine, e.g. monoethanolamine. Suitable ammonium salts for the second stage are ammonium sulphate or chloride, watersoluble salts of the amines mentioned above or of amines such as aniline or piperidine. Inert solvents may be present during the first stage, e.g. butanol, amyl alcohol, 2-ethyl-butanol or 2-ethyl hexanol. If the solvent boils below 100 DEG C. or if aqueous formaldehyde is used, a closed vessel must be employed. The reactants may be melted together without a solvent. If desired the acyclic body and the polyamine salt may be reacted first and the product reacted with the aldehyde, e.g. in presence of a diluent such as glacial acetic acid or tetrahydrofurfuryl alcohol. Advantageously boric acid may be added during the first stage condensation. The second stage condensation is preferably at 70-100 DEG C., if desired under super-atmospheric pressure. Water is the preferred solvent. It is preferably removed under reduced pressure to give a dry product. All three components may be reacted together or the product of the first stage condensation may be condensed with some or all of the aldehyde before condensation with the ammonium or amine salt. In Example 1, ethylene diamine hydrochloride is melted with dicyandiamide. Ammonia is split off. Boric acid is added, the mixture cooled a little and glacial acetic acid added and then paraformaldehyde. The mixture is cooled to about 100 DEG C., aqueous formaldehyde is added and the mixture refluxed, cooled and neutralized with sodium bicarbonate. The solution is then refluxed with ammonium chloride and aqueous formaldehyde. Drying under reduced pressure gives a colourless product soluble in hot water. Examples 2-4 are similar. In Example 5 dicyandiamide hydrochloride is used instead of ammonium chloride in the second stage, and in Example 6 diethylene triamine sulphate. The products are useful for improving the wet fastness of dyeings and prints (see Group IV (c). They may be used in conjunction with copper salts. Anti-creasing substances may also be included in the baths. Specification 738,647 is referred to.ALSO:Condensation products of acyclic compounds containing at least once the grouping <FORM:0814288/IV (c)/1> aldehydes and amine salts, with or without ammonium salts (see Group IV (a)), which are soluble in water at least in the form of their salts, are used for improving the wet fastness of dyeings and prints produced with water-soluble direct-dyeing dyestuffs containing sulphonic or carboxylic acid groups. The aqueous treating bath may contain a water-soluble copper compound, e.g. a salt or a complex copper compound, or a treatment with such a compound may follow the treatment with the condensation product. The materials dyed or printed may be of wool, silk, cotton, linen, artificial silk, or regenerated cellulose, e.g. staple fibres. After-treatment may be at room temperature or higher, e.g. 70-75 DEG C. The condensation products or mixtures thereof with copper salts may also be added to baths for imparting anti-crease effects to fabrics, thus producing anti-crease materials the dyeings on which have high fastness to washing. In Example 7, a cotton fabric dyed with the copper compound of the tris-azo dyestuff obtained by coupling the intermediate of tetrazotized benzidine and salicylic acid with the mono-azo dyestuff from diatotized 1-amino - 2 - oxybenzene - 5 - sulphonic acid and resorcinol is after-treated for 30 minutes at 20 DEG C. in a bath of 3000 parts of water and 2 parts of a condensation product from ethylene diamine hydrochloride, dicyandiamide, formaldehyde and ammonium chloride. Example 8 is similar, using a cotton fabric dyed with a stilbene azo-dyestuff obtained by condensing 1 mol. of dinitro-stilbene-disulphonic acid with one mol. of the azo-dyestuff from diazotized 1 - aminobenzene - 4 - sulphonic acid and 1-aminonaphthalene. Examples 10 and 11 are broadly similar, the after-treatment bath of Example 11 also containing copper sulphate. In Example 9 a fabric of regenerated cellulose staple fibres dyed with the symmetrical urea compound of the mono-azo dyestuff from diazotized 1 - amino - 8 - oxynaphthalene - 3,6-disulphonic acid and 1-amino-2-methoxy-5-methylbenzene is after-treated with an aqueous solution containing methylol urea, ammonium chloride, copper acetate and a condensate from ethylene diamine hydrochloride, dicyandiamide, formaldehyde and ammonium chloride. The fabric is rinsed and dried and has anti-crease properties and a dyeing with a high fastness to washing. Specification 738,647 is referred to.